|Publication number||US7830081 B2|
|Application number||US 11/748,195|
|Publication date||Nov 9, 2010|
|Filing date||May 14, 2007|
|Priority date||Mar 22, 2006|
|Also published as||US20070225464|
|Publication number||11748195, 748195, US 7830081 B2, US 7830081B2, US-B2-7830081, US7830081 B2, US7830081B2|
|Inventors||Larry Neil Lewis, Kelly Scott Chichak, James Anthony Cella, Joseph John Shiang|
|Original Assignee||General Electric Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (21), Non-Patent Citations (13), Referenced by (2), Classifications (12), Legal Events (2)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part of U.S. application Ser. No. 11/610,784, filed on Dec. 14, 2006 now U.S. Pat. No. 7,633,220 and U.S. application Ser. No. 11/610,765, filed on Dec. 14, 2006, now abandoned which claim priority from U.S. provisional application Ser. No. 60/784,750, filed Mar. 22, 2006. The entire contents of U.S. application Ser. No. 11/610,784, U.S. application Ser. No. 11/610,765, filed on Dec. 14, 2006, and U.S. provisional application Ser. No. 60/784,750, filed on Mar. 22, 2006 is incorporated herein by reference.
Organic light emitting diodes (OLEDs) are multi-layer optoelectronic devices. The current commercial applications for OLEDs are primarily in display applications These devices are composed of small molecules as the active materials. Manufacture of the small-molecule-based OLEDs relies heavily on vapor deposition processes. The next big application space for OLEDs is general lighting. In order to meet the large volume/low cost requirements for general lighting, low cost manufacturing processes like a roll-to-roll, newspaper-like printing are needed. Such roll-to-roll manufacturing employs solvent-based processes and thus small-molecules are replaced by good film-forming polymers. Processes that use successive solvent-based deposition steps suffer from the potential problem that the solvent used to apply one layer will remove the underlying polymer layer.
The first polymer based OLEDs were simple three-layer devices, limited to a cathode, an anode and an emissive layer, so as to minimize the issue of polymer removal by solvent. Naturally there has been a need to improve device performance thus necessitating the need for additional layers in the OLED.
The requirement for additional layers has led back to the problem of removal of underlying layers; wherein all layers are solvent-deposited. Two basic strategies have been applied to enable solvent-based deposition of multiple polymer layers. One can design a device where subsequent layers are deposited by solvents that do not remove the underlying layer. The prototypical example is that where the hole injection layer composed of poly(styrenesulphonate-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) is applied from water, the subsequent light emitting layer like 9,9-di-substituted polyfluorene, is deposited from solvents like xylenes; PDOT:PSS is not removed by xylenes. A second strategy for preparation of OLEDs with multiple layers deposited by solvents is to render each layer insoluble prior to application of the next layer. The second strategy can be divided into two types. A solvent soluble layer can be combined with a cross-linkable monomer like an acrylate. The desired layer and monomer is then subjected to conditions that cross-link the monomer, typically UV-irradiation. The result of the irradiation of the polymer layer and acrylate monomer is formation of an interpenetrating layer, rendering the solvent-deposited layer insoluble. A more elegant way to render a solvent-deposited layer insoluble is to custom-synthesize the layer of choice so that it contains a cross-linkable site; no added monomers are necessary. After deposition of the solvent-deposited layer, heat or light renders the layer insoluble.
However, there remains a need for methods and compositions that can render solvent-deposited layers insoluble for later deposition steps.
Hydrosilation of an organometallic compound of formula L2MZ can result in light emissive layers that are insoluble. In the formula, L and Z are independently bidentate ligands; at least one of L and Z comprises alkenyl, alkenylaryl, alkenyloxy, alkenyloxyaryl, alkynyl, alkynylaryl, alkynyloxy, alkynyloxyaryl, substituted alkenyl, substituted alkenylaryl, substituted alkenyloxy, substituted alkenyloxyaryl, substituted alkynyl, substituted alkynylaryl, substituted alkynyloxy, substituted alkynyloxyaryl, acrylate, methacrylate, or a combination thereof; and M is Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Ga, Ge, In, Sn, Sb, Tl, Pd, Bi, Po, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu.
In one aspect, the present invention relates to polysiloxanes derived from hydrosilation of an electrophophorescent organometallic compound of formula L2MZ. In particular embodiments, M is Ir, Os, Pt, Pd, Re, or Ru, and more particularly, M is Ir.
L and/or Z may be cyclometallated ligands, particularly those cyclometallated ligands that may be derived from phenylpyridine, tolylpyridine, benzothienylpyridine, phenylisoquinoline, dibenzoquinozaline, fluorenylpyridine, ketopyrrole, picolinate, acetylacetonate hexafluoroacetylacetonate, salicylidene, 8-hydroxyquinolinate, salicylaldehyde, iminoacetonate, 2-(1-naphthyl)benzoxazole)), 2-phenylbenzoxazole, 2-phenylbenzothiazole, coumarin, thienylpyridine, phenylpyridine, benzothienylpyridine, 3-methoxy-2-phenylpyridine, thienylpyridine, phenylimine, vinylpyridine, pyridylnaphthalene, pyridylpyrrole, pyridylimidazole, phenylindole, derivatives thereof or combinations thereof. In particular, L may be derived from 1-phenylisoquinoline, 2-phenylpyridine, a derivative thereof, or a combination thereof. More particularly, L may be derived from 2-phenylpyridine.
In particular embodiments, Z is derived from a ketopyrrole or substituted ketopyrrole, comprising at least one substitutent selected from alkenyl, alkenylaryl, alkenyloxy, alkenyloxyaryl, alkynyl, alkynylaryl, alkynyloxy, alkynyloxyaryl, substituted alkenyl, substituted alkenylaryl, substituted alkenyloxy, substituted alkenyloxyaryl, substituted alkynyl, substituted alkynylaryl, substituted alkynyloxy, substituted alkynyloxyaryl, acrylate, methacrylate, or a combination thereof. More particularly, Z may be derived from a ketopyrrole having at least one of the enumerated unsaturated substituents. Even more particularly, Z may be derived from a substituted 2-benzoylpyrrole.
The organometallic compound may be a compound of formula
q is 1 or 2.
In particular, R10 may be allyloxy. More particularly, the organometallic compound may be a compound of formula.
Organometallic compounds suitable for use in the polysiloxanes of the present invention are described in U.S. patent application Ser. No. 11/504,871, filed 16 Aug. 2006, Ser. No. 11/506,002, filed 17 Aug. 2006, Ser. No. 11/506,001, filed 17 Aug. 2006, Ser. No. 11/507,051, filed 18 Aug. 2006, Ser. No. 11/599,972, filed 15 Nov. 2006, Ser. No. 11/637,582, filed 12 Dec. 2006, Ser. No. 11/504,552, filed 14 Aug. 2006, Ser. No. 11/504,870 filed 16 Aug. 2006, Ser. No. 11/504,084 filed 14 Aug. 2006, all of which claim priority from U.S. Provisional Application Ser. No. 60/833,935, filed 28 Jul. 2006. The entire contents of the above patent applications is incorporated herein by reference.
In another aspect, the present invention relates to hybrid organic-inorganic polymer compositions derived from reaction between a hydrosiloxane and a polyfluorene comprising structural units of formula I
In particular embodiments, R2 may be C3-20 alkenyl, or C3-20 alkynyl, or C3-8 alkenyl, or C4-8 alkynyl, or R1 may be C3-C8 alkyl. In other embodiments, both R1 and R2 may be C3-20 alkynyl, or both R1 and R2 are C4-8 alkynyl. For example, the polymer composition may include polyfluorenes containing one or more of the structural units below:
Polysiloxanes according to the present invention may include structural units of formula I in addition to units derived from derived from hydrosilation of the organometallic compound of formula L2MZ.
In yet another aspect, the present invention relates to compounds or monomers from which the structural units of formula I may be derived. The monomers are of formula
Exemplary monomers according to the present invention include
Preferred substituents for R2a include C3-20 alkenyl, C3-20 alkynyl, C3-8 alkenyl, and C4-8 alkynyl. Preferred substituents for R1b are C3-C8 alkyl.
In another aspect, the present invention relates to polymers comprising structural units of formula
wherein R1a, R1b and R2a are as defined above.
Exemplary polymers according to the present invention include structural units of formula
Polyfluorenes for use in the polymer compositions of the present invention may include structural units in addition to those of formula I, such as unsubstituted fluorenyl units and/or fluorenyl units substituted with saturated groups such as alkyl. Other structural units may be derived from conjugated compounds as described in U.S. Pat. No. 6,900,285. In particular, structural units derived from tertiary aromatic amines may be used. The amount of structural units derived from unsaturated monomers ranges from about 0.05 mol % to about 50 mol %, particularly from about 1 mol % to about 25 mol %, and more particularly from about 1 mol % to about 10 mol %.
The polyfluorenes may be prepared by methods known in the art for making polyfluorenes, including Suzuki coupling of the appropriate dihalide and diboronate/diboronic acid and Yamamoto coupling. U.S. Pat. Nos. 5,708,130; 6,169,163; 6,512,083; and 6,900,285 describe synthesis of polymers containing fluorene subunits.
Any siloxane substituted with at least two hydrogen atoms may be used. In many embodiments, more than two hydro substituents are present. In particular, the hydrosiloxane may include structural units of formula
In various embodiments, n is an integer from 1 to 20, or R3 and R7, and/or R5 are H, or R9 is phenyl; or R4, R6, R8, and R10 are methyl. Exemplary hydrosiloxanes that may be used in the polymer compositions of the present invention include hydride terminated methylhydrosiloxane- phenymethylsiloxane copolymers, hydride terminated polydimethylsiloxanes, methylhydrosiloxane- dimethylsiloxane copolymers, polymethylhydrosiloxanes, polyethylhydrosiloxanes, hydride terminated polyphenyl-(dimethylhydrosiloxy)siloxanes, hydride terminated methylhydrosiloxane-phenymethylsiloxane copolymers, methylhydrosiloxane-octylmethylsiloxane copolymers, and hydride Q resins.
Vinyl siloxanes may be used in addition to the polyfluorenes and hydrosiloxanes in the polymer compositions of the present invention, if desired. Exemplary vinylsiloxanes that may be used in the polymer compositions of the present invention include vinyl terminated polydimethylsiloxanes, vinyl terminated diphenylsiloxane-dimethylsiloxanes, vinyl terminated polyphenylmethylsiloxanes, vinyl terminated trifluoropropylmethylsiloxane-dimethylsiloxanes, vinyl terminated diethylsiloxane-dimethylsiloxanes, trimethoxysiloxy terminated vinylmethylsiloxane-dimethylsiloxane copolymers, vinyl terminated vinylmethylsiloxane-dimethylsiloxane copolymers, vinyl Q resins and vinyl T-structure polymers.
Molecular weight of the hydrosiloxane and the vinylsiloxane is not critical, and typically ranges from about 200 to about 200,000 Daltons. The total amount of siloxane used ranges from about 1-50% by weight relative to the polyfluorene, and depends on the mol % of hydride in the hydrosiloxane, mol % of structural units derived from unsaturated monomers in the polymer, the amount of polymer in the composition, and, where a vinylsiloxane is used, on the mol % of vinyl groups in vinylsiloxane and the amount of vinylsiloxane in the composition. The stoichiometry ranges from less than about 1 moles of hydride to about 1 mole total unsaturation, that is including unsaturation in the polymer and in any vinylsiloxane, up to about 4.5 moles of hydride to about 1 mole unsaturation, and particularly from about 1.3 moles of hydride to about 1 mole unsaturation. Catalysts for the hydrosilation reaction include platinum complexes.
In yet another aspect, the present invention relates to optoelectronic devices comprising a polymer composition according to the present invention as at least part of an organic electroluminescent layer.
An opto-electronic device, exemplified by an organic light emitting device, typically comprises multiple layers which include, in the simplest case, an anode layer and a corresponding cathode layer with an organic electroluminescent layer disposed between said anode and said cathode. When a voltage bias is applied across the electrodes, electrons are injected by the cathode into the electroluminescent layer while electrons are removed from (or “holes” are “injected” into) the electroluminescent layer from the anode. Light emission occurs as holes combine with electrons within the electroluminescent layer to form singlet or triplet excitons, light emission occurring as singlet excitons transfer energy to the environment by radiative decay. An opto-electronic device according to the present invention includes an organic electroluminescent layer composed of the polymer composition of the present invention.
Other components which may be present in an organic light-emitting device in addition to the anode, cathode and light emitting material include hole injection layers, electron injection layers, and electron transport layers. The electron transport layer need not be in contact with the cathode, and frequently the electron transport layer is not an efficient hole transporter and thus it serves to block holes migrating toward the cathode. During operation of an organic light-emitting device comprising an electron transport layer, the majority of charge carriers (i.e. holes and electrons) present in the electron transport layer are electrons and light emission can occur through recombination of holes and electrons present in the electron transport layer. Additional components which may be present in an organic light-emitting device include hole transport layers, hole transporting emission (emitting) layers and electron transporting emission (emitting) layers.
The organic electroluminescent layer is a layer within an organic light emitting device which when in operation contains a significant concentration of both electrons and holes and provides sites for exciton formation and light emission. A hole injection layer is a layer in contact with the anode which promotes the injection of holes from the anode into the interior layers of the OLED; and an electron injection layer is a layer in contact with the cathode that promotes the injection of electrons from the cathode into the OLED; an electron transport layer is a layer which facilitates conduction of electrons from cathode to a charge recombination site. A hole transport layer is a layer which when the OLED is in operation facilitates conduction of holes from the anode to charge recombination sites and which need not be in contact with the anode. A hole transporting emission layer is a layer in which when the OLED is in operation facilitates the conduction of holes to charge recombination sites, and in which the majority of charge carriers are holes, and in which emission occurs not only through recombination with residual electrons, but also through the transfer of energy from a charge recombination zone elsewhere in the device. A electron transporting emission layer is a layer in which when the OLED is in operation facilitates the conduction of electrons to charge recombination sites, and in which the majority of charge carriers are electrons, and in which emission occurs not only through recombination with residual holes, but also through the transfer of energy from a charge recombination zone elsewhere in the device.
Materials suitable for use as the anode include materials having a bulk conductivity of at least about 100 ohms per square, as measured by a four-point probe technique. Indium tin oxide (ITO) is frequently used as the anode because it is substantially transparent to light transmission and thus facilitates the escape of light emitted from electro-active organic layer. Other materials which may be utilized as the anode layer include tin oxide, indium oxide, zinc oxide, indium zinc oxide, zinc indium tin oxide, antimony oxide, and mixtures thereof.
Materials suitable for use as the cathode include zero valent metals which can inject negative charge carriers (electrons) into the inner layer(s) of the OLED. Various zero valent metals suitable for use as the cathode 20 include K, Li, Na, Cs, Mg, Ca, Sr, Ba, Al, Ag, Au, In, Sn, Zn, Zr, Sc, Y, elements of the lanthanide series, alloys thereof, and mixtures thereof. Suitable alloy materials for use as the cathode layer include Ag—Mg, Al—Li, In—Mg, Al—Ca, and Al—Au alloys. Layered non-alloy structures may also be employed in the cathode, such as a thin layer of a metal such as calcium, or a metal fluoride, such as LiF, covered by a thicker layer of a zero valent metal, such as aluminum or silver. In particular, the cathode may be composed of a single zero valent metal, and especially of aluminum metal.
Materials suitable for use in hole injection layers include 3,4-ethylenedioxythiophene (PEDOT) and blends of PEDOT with polystyrene sulfonate (PSS), commercially available from H. C. Stark, Inc. under the BAYTRONŽ tradename, and polymers based on the thieno [3,4b]thiophene (TT) monomer, commercially available from Air Products Corporation.
Materials suitable for use in hole transporting layers include 1,1-bis((di-4-tolylamino) phenyl)cyclohexane, N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-(1,1′-(3,3′-dimethyl)biphenyl)-4,4′-diamine, tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine, phenyl-4-N,N-diphenylaminostyrene, p-(diethylamino) benzaldehyde diphenylhydrazone, triphenylamine, 1-phenyl-3-(p-(diethylamino)styryl)-5-(p-(diethylamino)phenyl)pyrazoline, 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane, N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine, copper phthalocyanine, polyvinylcarbazole, (phenylmethyl)polysilane; poly(3,4-ethylendioxythiophene) (PEDOT), polyaniline, polyvinylcarbazole, triaryldiamine, tetraphenyldiamine, aromatic tertiary amines, hydrazone derivatives, carbazole derivatives, triazole derivatives, imidazole derivatives, oxadiazole derivatives having an amino group, and polythiophenes as disclosed in U.S. Pat. No. 6,023,371.
Materials suitable for use as the electron transport layer include poly(9,9-dioctyl fluorene), tris(8-hydroxyquinolato) aluminum (Alq3), 2,9-dimethyl-4,7-diphenyl-1,1-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole, 1,3,4-oxadiazole-containing polymers, 1,3,4-triazole-containing polymers, quinoxaline-containing polymers, and cyano-PPV.
Materials suitable for use in the light emitting layer include electroluminescent polymers such as poly(9,9-dioctyl fluorene) and copolymers thereof, such as F8-TFB.
In the context of the present invention, alkyl is intended to include linear, branched, or cyclic hydrocarbon structures and combinations thereof, including lower alkyl and higher alkyl. Preferred alkyl groups are those of C20 or below. Lower alkyl refers to alkyl groups of from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, and includes methyl, ethyl, n-propyl, isopropyl, and n-, s- and t- butyl. Higher alkyl refers to alkyl groups having seven or more carbon atoms, preferably 7-20 carbon atoms, and includes n-, s- and t-heptyl, octyl, and dodecyl. Cycloalkyl is a subset of alkyl and includes cyclic hydrocarbon groups of from 3 to 8 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and norbornyl. Alkenyl and alkynyl refer to alkyl groups wherein two or more hydrogen atoms are replaced by a double or triple bond, respectively.
Aryl and heteroaryl mean a 5- or 6-membered aromatic or heteroaromatic ring containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; a bicyclic 9- or 10-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur; or a tricyclic 13- or 14-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from nitrogen, oxygen or sulfur. The aromatic 6- to 14-membered carbocyclic rings include, for example, benzene, naphthalene, indane, tetralin, and fluorene; and the 5- to 10-membered aromatic heterocyclic rings include, e.g., imidazole, pyridine, indole, thiophene, benzopyranone, thiazole, furan, benzimidazole, quinoline, isoquinoline, quinoxaline, pyrimidine, pyrazine, tetrazole and pyrazole.
Arylalkyl means an alkyl residue attached to an aryl ring. Examples are benzyl and phenethyl. Heteroarylalkyl means an alkyl residue attached to a heteroaryl ring. Examples include pyridinylmethyl and pyrimidinylethyl. Alkylaryl means an aryl residue having one or more alkyl groups attached thereto. Examples are tolyl and mesityl.
Alkoxy or alkoxyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, or cyclic configuration attached to the parent structure through an oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, and cyclohexyloxy. Lower alkoxy refers to groups containing one to four carbons. Alkenoxy, alkenyloxy, alkynoxy or alkynyloxy refers to groups of from 2 to 20 carbon atoms of a straight, branched, or cyclic configuration that include at least one double bond (for alkenoxy) or triple bond (for alkynoxy) and are attached to the parent structure through an oxygen. Examples include vinyloxy, propenoxy (allyloxy), hexenoxy, pentynoxy, and cyclohexenoxy.
Acyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent structure through a carbonyl functionality. One or more carbons in the acyl residue may be replaced by nitrogen, oxygen or sulfur as long as the point of attachment to the parent remains at the carbonyl. Examples include acetyl, benzoyl, propionyl, isobutyryl, t-butoxycarbonyl, and benzyloxycarbonyl. Lower-acyl refers to groups containing one to four carbons.
Heterocycle means a cycloalkyl or aryl residue in which one to two of the carbons is replaced by a heteroatom such as oxygen, nitrogen or sulfur. Examples of heterocycles that fall within the scope of the invention include pyrrolidine, pyrazole, pyrrole, indole, quinoline, isoquinoline, tetrahydroisoquinoline, benzofuran, benzodioxan, benzodioxole (commonly referred to as methylenedioxyphenyl, when occurring as a substituent), tetrazole, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furan, oxazole, oxazoline, isoxazole, dioxane, and tetrahydrofuran.
Substituted refers to residues, including, but not limited to, alkyl, alkylaryl, aryl, arylalkyl, and heteroaryl, wherein up to three H atoms of the residue are replaced with lower alkyl, substituted alkyl, aryl, substituted aryl, haloalkyl, alkoxy, carbonyl, carboxy, carboxalkoxy, carboxamido, acyloxy, amidino, nitro, halo, hydroxy, OCH(COOH)2, cyano, primary amino, secondary amino, acylamino, alkylthio, sulfoxide, sulfone, phenyl, benzyl, phenoxy, benzyloxy, heteroaryl, or heteroaryloxy.
Haloalkyl refers to an alkyl residue, wherein one or more H atoms are replaced by halogen atoms; the term haloalkyl includes perhaloalkyl. Examples of haloalkyl groups that fall within the scope of the invention include CH2F, CHF2, and CF3.
Many of the compounds described herein may contain one or more asymmetric centers and may thus give rise to enantiomers, diastereomers, and other stereoisomeric forms that may be defined, in terms of absolute stereochemistry, as (R)- or (S)-. The present invention is meant to include all such possible isomers, as well as, their racemic and optically pure forms. Optically active (R)- and (S)- isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. When the compounds described herein contain olefinic double bonds or other centers of geometric asymmetry, and unless specified otherwise, it is intended that the compounds include both E and Z geometric isomers. Likewise, all tautomeric forms are also intended to be included.
Oxaalkyl refers to an alkyl residue in which one or more carbons have been replaced by oxygen. It is attached to the parent structure through an alkyl residue. Examples include methoxypropoxy, 3,6,9-trioxadecyl and the like. The term oxaalkyl is intended as it is understood in the art, i.e. it refers to compounds in which the oxygen is bonded via a single bond to its adjacent atoms (forming ether bonds); it does not refer to doubly bonded oxygen, as would be found in carbonyl groups. Similarly, thiaalkyl and azaalkyl refer to alkyl residues in which one or more carbons has been replaced by sulfur or nitrogen, respectively. Examples include ethylaminoethyl and methylthiopropyl.
Silyl means an alkyl residue in which one to three of the carbons is replaced by tetravalent silicon and which is attached to the parent structure through a silicon atom. Siloxy is an alkoxy residue in which both of the carbons are replaced by tetravalent silicon that is endcapped with an alkyl residue, aryl residue or a cycloalkyl residue, and which is attached to the parent structure through an oxygen atom.
A bidentate ligand is a ligand that is capable of binding to metals through two sites. Similarly, a tridentate ligand is a ligand that is capable of binding to metals through three sites. Cyclometallated ligand means a bidentate or tridentate ligand bound to a metal atom by a carbon-metal single bond and one or two metal-heteroatom bonds, forming a cyclic structure, wherein the heteroatom may be N, S, P, As, or O.
To prepare copolymers of polyfluorenes with cross-linkable groups, a balance was struck between two factors. One approach is to prepare so-called F6-F or F8-F copolymers where F6 or F8 are di-hexyl or di-octyl fluorenyl units and F is a 9,9-un-substituted fluorenyl unit. Preparation of the desired copolymer from a mixture of 2,7-di-bromo and 2,7-di-boronic ester precursors via Pd-catalyzed Suzuki coupling afforded low molecular weight co-polymers in low yield as the proportion of the unsubstituted F unit increased above about 50%.
An alternative strategy used was to co-polymerize the appropriate 9,9-substituted monomers where possible. In some cases, where proportion of the alkynyl-substituted fluorene unit exceeded 5-10%, alkynyl-substituted monomers inhibited the Pd-catalyzed Suzuki reaction.
The (F6)3.0(F)1.0 copolymer precursor was prepared via Suzuki coupling and then subsequently reacted with an excess of a mixture of either hexylbromide/1-bromo-2-pentyne or a mixture of hexylbromide/allyl-bromide. Excess of R-Br relative to 9-hydrogens is desirable to ensure good conversion. The use of mixed alkyl-bromide with unsaturated bromide (allyl or alkyne) leads to final product with a distribution of saturated/unsaturated units on the 9-position (Scheme 1).
F6B2 and FBr2 were obtained from Aldrich and purified by recrystallization from acetonitrile. F6B2 was prepared from F6-bis-boronic acid and ethylene glycol. The product was purified by recrystallization from acetonitrile. F6B2 (2.5 g, 4.98 mmol), FBr2 (0.81 g, 2.5 mmol) and F6Br2 (1.23 g, 2.5 mmol) were combined with toluene (75 mL) under argon and then combined with stirring with K2CO3 (2.75 g, 20 mmol) and water (10 mL). After ca. 10 min, the catalyst ligand mixture was added composed of Pd(acetate)2 (0.030 g, 0.13 mmol) and tri-p-tolyl-phosphine (0.14 g, 0.46 mmol). The mixture was subjected to reflux overnight and then after cooling, the contents were filtered through a plug composed of roughly equal parts Celite, Drierite and 3-(diethylenetiramino)propyl-functionalized silica. The volatiles were removed in vacuo and then the residue was dissolved in toluene. A solid was precipitated with methanol; the toluene-insoluble fraction was dissolved in CH2Cl2 and precipitated into methanol.
(F6)3.0(F)1.0 (0.15 g, 0.13 mmol) was combined with hexyl bromide (0.21 g, 1.27 mmol) and allyl bromide (0.16 g, 1.32 mmol) in toluene (10 mL), Bu4NBr (0.01 g) and 50% NaOH (aq, 10 mL). The contents were subjected to reflux for 3 days. The aqueous layer was removed by pipette and then the top toluene layer was subjected to two 10 mL water extractions and then the toluene-solubles were poured into methanol to obtain a solid that was filtered and washed with methanol; 0.080 g obtained. 1H NMR showed that the 9-hydrogens in (F6)3.0(F)1.0 were consumed and that peaks due to allyl were present.
(F6)3.0(F)1.0 (0.1 g, 0.086 mmol) was combined with hexyl bromide (0.19 g, 0.0012) and allyl bromide (0.069 g, 0.57 mmol) in toluene (10 mL) and then Bu4NBr (0.01 g) was added with 50% NaOH (aq, 10 mL). The contents were subjected to reflux for 2 days under argon. After cooling the organic layer was extracted with water and then HCl (aq) and water. The toluene soluble layer was poured into methanol to obtain a precipitate that was dried in vacuo, 0.11 g.
(F6)3.0(F)1.0(0.24 g, 0.2 mmol) was combined with hexyl bromide (0.33 g, 2.0 mmol) and 1-bromo-2-pentyne (0.29 g, 1.99 mmol) in toluene (10 mL), Bu4NBr (0.01 g) and 50% NaOH (aq, 10 mL). The contents were subjected to reflux for 3 days. The aqueous layer was removed by pipette and then the top toluene layer was subjected to two 10 mL water extractions and then the toluene-solubles were poured into methanol to obtain a solid that was filtered and washed with methanol; 0.010 g obtained. 1H NMR showed the disappearance of the 9-H resonance.
Stock solutions of (F6)3.0(FR1R2)1.0, R1=allyl, R2=hexyl, moles of R1=2R2 were prepared (10 mg) in 1 mL of xylenes. Four samples were prepared on one-inch glass slides. For the first sample, the stock solution was spun on glass at 3000 rpm. For the second sample, the stock solution was spun on glass, as for the first sample. Both were baked at 140° C. for 15 minutes. Then the xylene solvent was spun on the second sample. Black light analysis clearly showed removal of polymer in the second sample, as compared to the first sample. For the third and fourth samples, a stock solution containing the same amount of the fluorene polymer in the same amount of xylenes, and 2 drops (ca. 0.1 g) of GE Silicones 88466, 1:1 copolymer of dimethyl siloxane methylhydrogen siloxane, was added along with 1 drop of a 0.15% platinum by weight solution of GE Silicones 88346 (Pt-tetramethyltetravinyltetrasiloxane complex in xylenes). A third sample was prepared by spinning on the solution on a glass slide and baking as for the first and second samples. The fourth sample was like the third, except that the xylene solvent was spun on after the baking step. Results are shown in Table 3.
TABLE 3 UV-Vis Measurements Sample No. Optical Density (OD) relative quantum efficiency (QE) 1 0.482 0.91 2 0.18 0.9 3 0.51 0.96 4 0.53 1
Optical measurements showed that samples 1, 3, and 4 were photophysically identical; sample 2 had about 60% loss. The variation between samples 1, 3 and 4 was probably due to their physical in-homogeneity rather than detected differences in QE or OD.
F6B2 (2.5 g, 5 mmol), F6Br2 (2.2 g, 4.5 mmol) and FBr2 (0.16 g, 0.5 mmol) were combined with toluene (75 mL) and Pd(acetate)2 (33 mg, 0.15 mmol), tri-o-tolyl-phosphine 0.16 g, 0.53 mmol). The solution was stirred under argon and then E4NOH (18.4 mL of a 20% solution) and water (18 mL) was added with stirring and heating for 24 h. The solution was extracted with water, 10% HCl, water, saturated NaCl and water. The toluene-solubles were stirred with Celite, Drierite and 3(diethyltriamino)propyl-functionalized silica and then filtered. The volatiles were removed in vacuo to obtain 4.48 g crude polymer, Mn=12,800, Mw=37,900. The polymer was twice re-precipitated with toluene and methanol to obtain a solid with Mn=11,300 and Mw=28,500. 1H NMR integration of the 9-H protons of the F unit vs. the first methylene units of the F8 group show a mole ratio of these units of 4:96.
The following components of the Yamamoto catalyst (H. Q. Zhang, Thin Solid Films, 477 (2005) 119) were combined: zinc powder (0.7 g, 11 mmol), triphenyl phosphine (0.75 g, 2.86 mmol), 2,2′-bipyridine (0.056 g, 0.36 mmol) and NiCl2 (0.046 g, 0.36 mmol) in dimethylformamide (dmf, 25 mL) and degassed under argon. Then the monomers F8 Br2 (1 g, 1.82 mmol) and FBr2 (0.91 g, 1.82 mmol) were combined and the mixture was subjected to heating at 100° C. with stirring under argon for 17 h. THF was added to the mixture (some losses) and the contents filtered to remove catalyst. The filtrate was poured into methanol to give a green solid product. The product was re-precipitated with CH2Cl2 and methanol. 1H NMR analysis showed that the ratio of F to F8 was about 1:1.2.
2,7-dibromofluorene (5 g, 15.4 mmol) was combined with 1-bromo-5-hexene (7.5 g, 46.0 mmol) in toluene (50 mL), NaOH (50 mL, 50%, aq) and Bu4NBr (0.1 g) as a phase transfer catalyst. The mixture was heated at ca. 100° C. with stirring for 5 h. The organic layer was separated from the aqueous layer and then treated with 10% HCl and then water and then stirred the MgSO4 and carbon black. The solution was filtered and all solvents were removed in vacuo to give a brown oil, 7.83 g.
2,7-dibromofluorene (5 g, 15.4 mmol) was combined with allyl bromide (5.6 g, 46.2 mmol) and reacted with toluene, NaOH and Bu4NBr as above for 2,7-dibromo-9,9-dihex-5-enyl-fluorene. 7.1 g of a yellow solid was obtained.
2,7-Ethyleneglycolateboronic ester-9,9-dihexylfluorene (2.5 g, 5 mmol), 2,7-dibromo-9,9-di-hex-5-enyl-fluorene (0.3 g, 0.61 mmol), 2,7-dibromo-9,9-diallyl-fluorene (0.7 g, 1.74 mmol) and 2,7-dibromo-9,9-hexyl-fluorene (1.23 g, 2.5 mmol) were combined in toluene (75 mL), Pd(PPh3)4 (140 mg) and Et4NOH (25%, 10 mL). The mixture was heated with stirring at 80° C. for 24 h. The mixture was filtered through a 1:1:1 (w/w/w) mixture of Celite, Drierite and 3(diethyltriamine)propyl-functionalized silica. The filtrate was taken to dryness in vacuo and then dissolved in a minimum of toluene. The toluene solution was poured into methanol to obtain a orange solid which was collected by filtration and washed with methanol. The obtained solid was re-precipitated to obtain 2.14 g of solid, gpc Mw=35,000. Mn=10,600.
Platinum Irgafos Complex: Platinum Karstedt catalyst (complex of Pt0 with divinyltetramethyldisiloxane, 5% Pt in xylenes, 0.25 g, 1.28 mmol Pt), vinyl-stopped polydimethylsiloxane (GE 88934, 3.3 g) and Irgafos 168 (tris-(2,4-di-t-butylphenyl) phosphate, Ciba Geigy; 3.31 g, 5.12 mmol) were combined with toluene (50 mL) and refluxed overnight. The volatiles were then removed in vacuo to give 6.76 g of a white oil, estimated 3.7% Pt. A stock solution of the Pt Irgafos catalyst was prepared with 0.135 g in xylenes (50 mL volumetric flask); 0.1 mg Pt/mL.
A stock solution was prepared containing PMV 9925 (Gelest; 20 g) and HPM 502 (Gelest; 2.8 g).
The PMV/HPM stock solution (1 g) and the Pt Irgafos catalyst (10 uL) were combined with (F6)3.0(Fpentyne)1.0 fluorene copolymer (20.7 mg). No gel formed upon heating in deuterated benzene. The experiment was repeated except that (F6)3.0(Fallyl)1.0 (19.5 mg) was heated in deuterated benzene and gelled, insoluble in benzene after heating. The experiment was repeated except that (F8)0.9(Fallyl)0.1 (15.1 mg) was combined with the stock solution and heated in deuterated benzene to give an insoluble gel. 1H NMR analysis confirmed that vinyl was consumed in the solutions containing gelled polymers.
To a stirred CH2Cl2 solution (5 mL), maintained at −78° C. and under an atmosphere of N2, was added 2.2 mL of BBr3 (1 M in CH2Cl2) followed by the dropwise addition of 3 (200 mg, 0.864 mmol) dissolved in CH2Cl2 (1 mL). The cooling bath was removed and the reaction mixture was allowed to warm to room temperature overnight with stirring. The reaction mixture was then poured into a separatory funnel containing H2O (20 mL) and EtOAc (20 mL). The layers were separated and the H2O layer was extracted with EtOAc (2×15 mL). The combined organic extracts were dried over Na2SO4, filtered and finally concentrated to dryness affording a sticky solid. Yield (135 mg, 77%). 1H NMR (400 MHz, CD3OD, 25° C.) δ 6.28 (m, 1H), 6.45 (t, 1H), 6.73(d, 2H), 6.88 (m, 1H), 7.15 (m, 1H); 13C NMR (100 MHz, CD3OD, 25° C.) δ 107.0, 108.5, 111.6, 121.5, 127.5, 132.3, 142.1, 159.8, 187.0; HRMS (EI): m/z 203.0560 (100) [M]+.
To a solution of the bisphenol of Example 12 (100 mg, 0.492 mmol) in DMF (2.0 mL) were added successively potassium carbonate (272 mg, 1.97 mmol) and allyl bromide at room temperature. The mixture was stirred for 24 h, poured into water, and then extracted with Et2O. The extract was washed with brine, dried over Mg2SO4, and concentrated to dryness. The resulting residue was chromatographed through silica gel (CH2Cl2) to give the product as a colorless oil. Yield (123 mg, 88%). 1H NMR (400 MHz, CD2Cl2, 25° C.) δ 4.58 (m, 4H), 5.30 (m, 2H), 5.43 (m, 2H), 6.08 (m, 2H), 6.34 (m, 1H), 6.70 (t, 1H), 6.92 (m, 1H), 7.03 (d, 2H), 7.17 (m, 1H), 9.83 (bs, 1H); 13C NMR (100 MHz, CD2Cl2, 25° C.) δ 69.7, 106.1, 108.2, 111.5, 118.0, 119.7, 125.9, 131.6, 133.7, 140.8, 160.2, 184.4; HRMS (EI): m/z 283.1179 (100) [M]+.
To a stirred 2-methoxyethanol solution (4 mL) containing the ketopyrrole of Example 13 (115 mg, 0.406 mmol) was added solid sodium hydride (40.0 mg, 1.67 mmol) causing the solution to turn yellow in color. After letting this solution stir for 5 min, [(piq)2Ir(μ-Cl)]2 (211 mg, 0.162 mmol) was added and the mixture was then heated at 80° C. for 1.5 hrs. The dark red reaction mixture was cooled to room temperature and poured into MeOH (150 mL) causing the product to precipitate. The product was collected by filtration, washed with MeOH, and dried in air. Yield (270 mg, 94%). 1H NMR (400 MHz, CD2Cl2, 25° C.) δ 4.51 (m, 4H), 5.24 (m, 2H), 5.35 (m, 2H), 6.00 (m, 2H), 6.29 (m, 1H), 6.41 (m, 1H), 6.46 (m, 1H), 6.53 (t, 1H), 6.61 (t, 1H), 6,74 (m, 1H), 6.78 (m, 1H), 7.00 (m, 4H), 7.18 (m, 1H), 7.33 (d, 1H), 7.46 (d, 1H), 7.51 (d, 1H), 7.73 (m, 4H), 7.91 (m, 2H), 8.26 (m, 2H), 8.33 (d, 1H), 8.99 (m, 2H); HRMS (MALDI): m/z 883.2067 (100) [M]+.
A stock solution was prepared containing PMV 9925 (20 g) and HPM 502 (2.8 g). The stock solution (1.0 g) was combined with the Iridium compound of Esample 14 (8.5 mg) and 10 uL Pt Irgafos (1 mg/mL) in C6D6 (1 mL). The contents were heated in an NMR tube at 80° C. for 1 h at which point an insoluble red gel formed with all vinyl and hydride consumed as shown by NMR.
A fluorene polymer containing 96 mol % F8-TFB and 4 mol % F8- Fphenyloxyallyl (49.2 mg), the iridum compound of Example 14 (2.6 mg), HPM 502 (2.2 mg), stock Pt Irgafos solution (5 uL) were dissolved in 1 mL C6D6 in an NMR tube. The tube was heated for 20 min at 120° C. 1H NMR showed consumption of all vinyl and SiH resonances yet the contents remained soluble in benzene.
While only certain features of the invention have been illustrated and described herein, many modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.
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|U.S. Classification||313/504, 528/28, 528/25, 528/27, 528/31, 313/503|
|International Classification||H01J1/62, C08G77/398|
|Cooperative Classification||C08G77/58, G02B1/043|
|European Classification||C08G77/58, G02B1/04B2|
|May 14, 2007||AS||Assignment|
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LEWIS, LARRY NEIL;CHICHAK, KELLY SCOTT;CELLA, JAMES ANTHONY;AND OTHERS;REEL/FRAME:019289/0887
Effective date: 20070514
|May 9, 2014||FPAY||Fee payment|
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